Recent advances during CH4 dry reforming for syngas production: A mini review

Given the continuing issues of environment and energy, methane dry reforming for syngas production have sparked interest among researchers, but struggled with the process immaturity owing to catalyst deactivation. This review summarizes the recent advances in the development of efficient and stable catalysts with strong resistance to coking and metal sintering, including the application of novel materials, the assessment of advanced characterizations and the compatibility to improved reaction system. One feasible option is the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a fine metal dispersion and surface confinement effect via a metal exsolution strategy and exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also extend the option because of their unique morphology and microstructure. It also is elaborated that progresses were achieved in advanced characterizations application, leading to success in the establishment of reaction mechanisms and attributions to the formed robust catalysts. In addition, the perspective described the upgrade of reaction system to a higher reaction efficiency and milder reaction conditions. The combination of efficient reaction systems and robust catalysts paves a way for a scaling-up application of the process.     

Pulsed KrF excimer laser annealing of silicon solar cell

The pulsed KrF excimer laser annealing of silicon films for solar cell with EBEP-CVD and LP-CVD was studied theoretically and experimentally. Three-dimensional thermal diffusion equation for microcrystalline and amorphous silicon was solved by using the finite difference methods. The results of our heat-flow simulation of laser re-crystallization in a laser irradiation with 50 ns pulse duration almost agree with the experimental results in re-crystallization depth of 0.7 μm for microcrystalline silicon (EBEP-CVD) and 0.4 μm for amorphous silicon (LP-CVD) in a single pulse excimer laser annealing.     

Equilibrium and crystallographic measurements of the binary tetrahydrofuran and helium clathrate hydrates

Clathrate compounds are crystalline materials formed by a physical interaction between host and relatively light guest molecules. Various types of nano-sized cages surrounded by host frameworks exist in the highly unique crystalline structures and free guest molecules are entrapped in an open host-guest network. Recently, we reported two peculiar phenomena, swapping and tuning, naturally occurring in the hydrate cages. Helium, one of the smallest light guest molecules, must be the challengeable material in the sense of physics and moreover possesses versatile applications in the field of superconductivity technology and thermonuclear industry. In this regard, we attempted for the first time to synthesize helium hydrates at moderate temperature and pressure conditions. According to inclusion phenomena, helium itself normally cannot form clathrate hydrates due to being too small molecularly without the help of hydrate former molecules (sI, sII, and sH formers). In this study, the hydrate equilibria of the binary clathrate hydrate containing tetrahydrofuran, helium, and water were determined at 2, 3, 5.56 THF mol%. Direct volumetric measurements were also carried out to confirm the exact amount of helium captured in the hydrate cages. Finally, the crystalline structure of the formed mixed hydrates was identified by powder X-ray diffraction, resulting in structure II.     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

Infrared absorption in Li-intercalated tungsten oxide

Thin films of amorphous and polycrystalline tungsten oxide were produced by reactive dc magnetron sputtering and nanocrystalline films were deposited by advanced gas evaporation. The films were submitted to electrochemical intercalation of Li ions before infrared reflectance measurements were carried out. For crystalline films, the reflectance in the wavelength region 10–30 μm increases upon intercalation, indicating an increasing free-electron contribution. On the other hand, all the films display an increased absorption at wavelengths less than 10 μm when intercalated. The thermal emittance could be varied from about 0.5 to 0.7–0.75 by intercalation in films with thicknesses in excess of 1 μm. Both absorption and interference contribute to the emittance contrast.     

深过冷Fe76B12Si12超细晶材料的凝固组织与软磁性能

首次采用深过冷加水淬的方法,成功地制备了直径为16 mm的样品,高为15 mm,组织中颗粒平均尺寸约为120nm左右的Fe76B12Si12合金超细晶材料.其磁损耗P1T400和P1T1000分别为普通硅钢片的40%和65%.系统研究了组织类型及Fe2B(Si)相尺度对该合金软磁性能的影响,发现该合金的最佳软磁性能位于Fe2B(Si)相完全粒化的非规则共晶组织区,并且当Fe2B(Si)相尺寸细化至0.36～0.50μm时,其软磁性能随着相尺寸的减小而大幅度改善.对以上结果产生的原因进行了讨论.     

Tetragonal structure, anionic vacancies and catalytic activity of SO4-ZrO2 catalysts for n-butane isomerization

An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO₄²⁻-ZrO₂ with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO₄²⁻-ZrO₂ catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H₂ was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work.

A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO₄²⁻-ZrO₂ is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.     

低压片状模塑料增稠工艺研究

采用氧化镁为增稠剂、结晶树脂以粉料形式加入而降低片材热模内粘度的工艺，改进了对低压片状模塑料的增稠方法。结果表明：采用此工艺，设备不需要加热，增稠符合传统SMC增稠曲线；片材在模腔内有较低的粘度，适宜于低压成型。     

Self-assembly and crystallization behavior of a double-crystalline polyethylene-block-poly(ethylene oxide) diblock copolymer

The self-assembly and crystallization behavior of a well-defined low molecular weight polyethylene-block-poly(ethylene oxide) (PE-b-PEO) diblock copolymer was studied. The number-average degrees of polymerization for the PE and PEO blocks were 29 and 20, respectively. The molecular weight distribution was 1.04 as determined by size-exclusion chromatography. The PE-b-PEO sample exhibited two melting points at 28.7 and 97.4 °C for the PEO and the PE crystals, respectively. The crystallization of the PE blocks was unconfined, while the crystallization of the PEO blocks was confined between pre-existing PE crystalline lamellae, as demonstrated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) studies. In the fully crystalline state, both PE and PEO blocks formed extended-chain crystals with PE chains tilted ∼22° from the lamellar normal and PEO chains parallel to the lamellar normal, as evidenced by two-dimensional WAXD study of shear-oriented samples. Regardless of hydrogen bonding among hydroxyl chain ends in the PEO blocks, interdigitated, single-crystalline layer morphology was observed for both PE and PEO crystals. The partial crystalline morphology, where the PE crystallizes and the PEO is amorphous, had the same overall d-spacing as the fully crystalline morphology. A double-amorphous PEO layer sandwiched between neighboring PE crystalline layers was deduced based on a chain conformation study using Fourier transform infrared. The confined crystallization kinetics for PEO blocks was investigated by differential scanning calorimetry, which could be explained by a heterogeneous nucleation mechanism. The slower crystallization rate in the PEO-block than the same molecular weight homopolymer was attributed to the effects of nanoconfinement and PEO chains tethered to the PE crystals.